New cupriferous trisazo dyestuffs



1 that splitting up of the O-alkyl groups takes Patented Aug. 10, 1954 UNITED STATES PATENT OFFICE NEW CUPRIFEROUS TRISAZO DYESTUFFS Raymond Gunst, Binningen, Switzerland, as-

signor to Ciba Limited, Basel, Switzerland, a Swiss firm N Drawing. Application February 2, 1953, Serial No. 334,713

Claims priority, application Switzerland August 25, 1949 I 7 Claims. (01. 260-146) 1 2 This application is a continuation in part of benzene-2-carboxylic acid itself. The so-obmy copending application Serial No. 180,697, tained diazo azo compound is then coupled in an filed August 21, 1950. The present invention is acid medium with a l-amino-benzene or a 1- based on the observation that the cupriferous aminonaphthalene containing in its 2-position trisazo dyestuffs of the formula c an alkoxy group of low molecular weight such 1 oou- -o N\ S0311 B A hanmraipim NH C HOaS- S are very valuable dyestuffs. The molecule of these dyestuifs contains a single complex-bound The amino disazo dyestufis thus obtained are copper atom and in the Formula 1, R1 represents then diazotized and coupled with 2-[4-(8"-hya benzene radical containing a hydroxyl group droxynaphthyl-[2"l-aminophenyl)l-fi-methylin para-position with respect to the azo group benzthiazole-X:6"-disulfonic acid. As amines and a carboxylic acid group in ortho-position to yielding the radical the hydroxyl group, and R2 represents a benzene as for example an ethoxy or a methoxy group.

or naphthalene radical to which the groups O-alkyl R, (A) N=N there come into consideration amines of the benzene series, such as 1-amino-2-methoxy-benzene (B) or 1-amino-2:5-dimethoxy-benzene, and also I amines of the naphthalene series, such as for inare bound in 1:2:4-position. stance 1-amino-2-methoxyor -ethoxynaphtha- The cupriferous trisazo dyestufis of the Forlene and especi y yp mula 1 can be obtained by subjecting trisazo dyelene-6- or -7-sulfonic acids. A method for the studs which correspond to the formula preparation of 2-[4-(8-hydroxynaphthy1-[2"]- 2 ,i O -alkyl HO /N\ 50311 Rpanmrathn wage CH3 HOaS- s in which R1 has the meaning given above and R2 represents a benzene or naphthalene radical to aminophenyl) l-fi-methyl-benzthiazole-X 6 -di 'sulfonic acid corresponding to the formula which the groups O-alkyl and are bound in 1:2:4-position, to the action of an agent providing copper; under conditions such V v H O N\ S 0 3H CH3 HOsS S is given in example below.

According to the present invention the trisazo dyestuffs of the Formula 2 are to be treatedin place with the formation of the ortho:orthodihydroxyazo copper complexes. with splitting up of the alkoxy group bound to The trisazo-dyestufis of the Formula 2 can be the radical R2 the corresponding ortho:orthoobtained as follows: tetrazotized 4:4-diaminodidihydroxy copper complex is produced which phenyl is coupled on one side in a medium rencontains a single atom of complex-bound copper dered alkaline with alkali carbonate with a hyin the dyestufi molecule, and therefore contains droxybenzene-ortho-carboxylic acid capable of no copper bound in complex union with the radicoupling, such as for example fi-methyl-l-hycal R1. For this reason it is of advantage to droxybenzene-2-carboxylic acid or l-hydroxyemploy per molecular proportion of dyestuff such a way with an agent providing copper that about the quantity of the agent providing copper parts of water. Then 7.5 parts of sodium nitrite which contains one gram atom of copper. Methare added and diazotization is brought about by ods which lead to a dealkylating coppering are adding 60 parts of hydrochloric acid of 30 per known. In many cases that process has proved cent. strength at 5-10 C. The sparingly soluble especially suitable according to which, with the 5 diazo compound is filtered oii, suspended again application of copper tetrammine complexes in in water and then coupled with 55 parts of 2- the presence or absence of an excess of ammonia [=l'- 8" hydroxynaphthyl-[2"] aminophenor an organic base, such as pyridine or ethanolyl) l-6-methyl-benZthiazole-X:6-disu1fonic acamine, the coppering is carried out in an aqueous id in the presence of 30 parts of sodium carbo medium for several hours at a temperature in 10 nate and 150 parts of pyridine. The trisazo dyethe neighborhood of 100 C. stuff is salted out with sodium chloride, filtered With regard to the formuiae of the cupriferous ofi and separated from any impurities better dyestufis it should be explained that these i'orsoluble than the dye by washing it with diluted mulae undoubtedly represent the correct stoisodium chloride solution. chiometric quantities of copper and the correct In order to transform it into the complex copposition of the copper atom in the complex, but per compound the trisazo dyestufi is dissolved in the distribution of the main and secondary 1400 parts of water and 100 parts of pyridine, an valences in the complex union of the copper has aqueous ammoniacal solution of cupric tetramnot yet been established with certainty. mine sulfate, the copper content of which cor- The new cupriferous trisazo dyestuffs of the responds to parts of crystallized copper sul- Formula 1 can be employed for the dyeing and fate, is added and the whole is stirred for 5 hours printing of a wide Variety of materials, such as at 9D95 C. By carefully neutralizing the reacwool and silk, but especially fibers containing tion mixture by the addition of hydrochloric cellulose, such as cotton, linen and also artiacid the complex copper compound of the forficial silk and staple fibers of regenerated cellu- 25 mula (l)--Gu(|) /N SOaH -CH3 H000 H038 s H038 lose. Very interesting shades are obtained of precipitates. It is filtered off and dried and very good fastness to light. then forms a dark powder which dissolves in wa- In the following example the parts and perter with a greyish green coloration and dyes celcentages are by weight unless otherwise stated, lulosic fibers olive tints having good fastness the relation between parts by weight and parts properties. by volume being the same as that between the Dyestuffs of similar properties are obtained kilogram and the liter. when, in the present example, G-methyl-l-hy- Example drcXybenzene-2-carboxylic acid is used instead of 1-hydroxybenzene-2-carboxylic acid or when 1 parts of 4:4'-d1amm0d p y1 are tetthe 1-amino-z-methoxynaphthalene 6 sulrazotized in known manner and the tetrazo comionic acid is replaced by l-amino-2-methoxypound 18 coupled with 15 parts of l-hydroxybennaphthalene-7-sulfonic acid. These dyestufis zene-2-carboxyl1c acid in an aqueous medium correspond to the formulae H3? ?Cl1 (I) N\ SOaH no N: M Na. NH

A) CH; 1100 H038 8 and C')-Gu o /N sour cm Hooc H035 s SOsH alkaline with sodium carbonate. Acetic acid is Dyestuffs of similar properties but yielding added to the so-obtained yellowish-brown susbrown tints with an olive cast are obtained, when pension until it reacts weakly acid to litmus pain the present example 1-amino-2-methcxyper and the diazo-azo compound is then coupled naphthalene sulfonic acid is replaced by l-amiwith 25.3 parts of i-amino-Z-methoxynaphthano-2-methoxybenzene or 1-amino-2z5-dimethlene-G-sulfomc acid. The disazo-dyestufi is oxybenzene. These dyestuffs correspond to the then filtered off and suspended again in 1600' formulae (|)-Ou 0 /N\ SOaH CH3 B000 s :3

and

The 2-[4'-(8"-hydroxynaphthyl [2"l-aminophenyl)] 6 methyl benzthiazoleX:6-disulfonic acid used as starting material in this example can be produced as follows:

24.0 parts of 1:7-dihydroxynaphthalene-3- sulfonic acid are suspended in 500 parts of commercial sodium bisulfite solution. At 95 C'., 46 parts of 2 (4 aminophenyl) 6 methylbenzthiazole-X-sulfonic acid (obtained by sulfonation of 2 (4' aminophenyD-S-methylbenzthiazole with fuming sulfuric acid) are introduced and the reaction mixture is maintained for 60 hours with stirring and reflux cooling at 95-97 0. After cooling, the condensation product which is diflicultly soluble in acid solution, is

filtered ofi. For purification the filter residue 1 dissolved in the hot in a medium alkaline with sodium carbonate and freed from any insoluble residue by filtration. By addition of dilute hydrochloric acid the condensation product is precipitated as an orange-brown deposit. If desired the condensation product can be freed from sulfurous acid by heating the suspension, until the sulfurous acid has completely evaporated.

What is claimed is:

1. A cupriferous trisazo dyestuff containing a single-copper atom bound in complex union with the dyestuff molecule and corresponding to the formula HOOC HO O 0 H03 in which R1 represents a benzene radical con- 10 taining a hydroxyl group in para-position with respect to the azo group and a carboxylic acid group in ortho-position to the hydroxyl group, and R2 represents a mononuclear aromatic radical containing at the most two condensed rings and to which the groups are bound in 1:2:4-position.

2. A cupriferous trisazo dyestuff corresponding to the formula wherein R2 represents a benzene radical to which the groups N=N -OCu-- and di itare bound in 1:2:4-position.

3. A cupriferous trisazo dyestufi corresponding to the formula SOaH CH; HOaS S wherein one X stands for hydrogen and the other X stands for a sulfonic acid group.

4. The cupriferous trisazo dyestufi of the formula.

5. The cupriferous trisazo dyestufi of the formula OCu0 I v /N\ SOIH N S G 6. The cupriferous trisazo dyestufi of the formula OCu 0 N 80,11

CH8 H000 Hmss 7. The cupriferous trisazo dyestufi of the formula (])Ou O N SOaH Q @G G H0 N=N N=N N=N NH 0\ CH3 HOOC HaC HOaS S No references cited. 

1. A CUPRIFEROUS TRISAZO DYESTUFF CONTAINING A SINGLE-COPPER ATOM BOUND IN COMPLEX UNION WITH THE DYESTUFF MOLECULE AND CORRESPONDING TO THE FORMULA 